Paper coating compositions and paper coated therewith

ABSTRACT

An aqueous pigment coating composition essentially containing water-soluble modified polyvinyl alcohol as a coating binder having one kind or plural different kinds of substituent group selected from cyanoethyl group, carbamoylethyl group, carboxyethyl group, sodium carboxyethyl group, potassium carboxyethyl group, ammonium carboxyethyl group, carboxymethyl group, sodium carboxymethyl group, potassium carboxymethyl group and ammonium carboxymethyl group. The coating color has a proper flow property and provides a pattern-free and smooth surface onto a coated paper.

United States Patent 11 1 Akiyama et a1.

1 1 3 8 45 Jan. 30, 1973 [54] PAPER COATING COMPOSITIONS AND PAPER COATED THEREWITH [75] Inventors: Toyomi Akiyama, Sakai, Osaka; Mitsuru Kondo, Hyogo; Satoshi Dotani, Toyonaka, Osaka, all of [21] Appl. No.1 854,767

[30] Foreign Application Priority Data Sept. 2, 1968 Japan .43/62891 [52] 11.8. C1. ..117/155 UA,1- 17/156, 117/161 UE, 7 260/913 VA [51] lnt. Cl....- ..D2lh l/32 [58] Field of Search ..117/155 UA,156,161UE; v 260/91 3 VA [56] I References Cited UNITED S TATESPATENTS' 2,759,847 8/1956 Frost et a1 ..117/155 X 2,919,205 12/1959- Hart ..117/155 x 3,218,191 11/1965 Domanski..... ..117/155 X "Dorland et a1 ..117/155 X 3,228,327 1/1966 Heffner ..117/155 X 3,329,525 7/1967 Powers 3,375,121 3/1968 Bildusas 3,476,582 11/1969 lmoto et a1. ..117/155 X 3,477,970 11/1969 Beeman ..117/155 X 3,481,764 12/1969 Matsumoto et a1 ..117/155 X 3,316,190 4/1967 Suzumura et a1..... ..260l32.2 3,324,057 6/1967 Suzumura et a1. ....l17/155 X 3,365,408 1/1968 Ohara ...260/91.3 X 3,148,166 9/1964 Suzumura et a1. ..260/91.3 X

Primary Examiner-William D. Martin Assistant ExaminerM. R. Lusignan Attorney-,Cushman, Darby & Cushman 57 ABSTRACT An aqueous pigment coating composition essentially containing water-soluble modified polyvinyl alcohol as a coating binder having one kind or plural different kinds of substituent group selected'from cyanoethyl group, carbamoylethyl group, carboxyethyl group, sodium carboxyethyl group, potassium carboxye thyl group, ammonium carboxyethyl group, carboxymethyl group, sodium carboxymethyl group, potassium carboxymethyl' group and ammonium carboxymethyl group, The coating color has a proper flow property and provides a pattern-free and smooth surface onto a coated 'paper.

3Claims, No Drawings protein, synthetic resin emulsion such as styrene-bu- V tadiene polymer, acrylic resins, polyvinyl acetate and modified starch. Combinations of adhesives are sometimes used.

The requirements of a coating composition for coating paper to be used for high quality printing are quite severe. Of utmost importance, the dried coating must serve a smooth printing surface having uniform and controllable ink acceptance. Secondly, the coating film must have sufficient internal strength and must be bonded to a cellulosic fiber of the paper substrate so as to resist flaking and picking during handling and, more particularly, during the high speed printing process. And further, the coating must provide opacity and brightness to the sheet and should accept a gloss when supercalendered. in addition to the requirement described above pertaining to the final properties of the coated paper, the coating composition must possess suitable rheological properties vforproper application from the coating station to the paper surface.

Coating binders exert a tremendous influence on the properties of both the coating composition and the final coated paper. The binder in the-pigment coating l )providesa suspending medium for the pigment; (2

. imparts the desirable rheological properties to the coating composition (3) serves as a binder for the pigment particles in the dried coating; (4) binds thepigment particles to the base; (5.) provides a smooth and continuous printing surface with uniform and controllable ink acceptance. I I

One most important property of the coating binder is the pigment bonding strength, since this property determines the amount of binder necessary to hold the pigment on the paper. Each grade of coated paper has a definite strength requirement, and the amount of binder necessary in the coating'to meet this requirement is determined by the pigmentbondin'g strength of the binder. The higher the pigment bonding strength of the. hinder, the higher the ratio of pigmentto binder that is possible, and the better the opacity, brightness and gloss of the paper. If the ratio of binderto pigment is too high, the quality of the paper is poor. Another important property of the coating binder is the proper rheological property'to thecoating composition as well as pig ent bonding strength. Therefore, great care must be taked to select the proper pigment and binder and to use'them together in proper balance to obtain the desired coated product. The binders commonly used heretofore are normally employed in amounts of -30 parts binder per 100 perts of pigment. Polyvinyl alcohol (hereinafter preferred to as PVA) is a very powerful pigment binder. This means that a relatively small amount of PVA is required to obtain a coating that adequate .strength to be commercially useable. Generally, thehigher the degree of polymerization of PVA the stronger the bonding strength becomes and the viscosity is increased at the same time. Espesuitableflo'w properties in the above cially, PVAhaving average degree of polymerization 7) of more than 800 and more than 88 percent hydrolysis is used for properbonding strength. For example, the PVA having average degree of polymerization of 1700 and 99-100 percent hydrolysis enables one to obtain a similar bonding strength with only one-third of the quantity which would be necessitated by casein or soy protein and one-fourth of the quantity necessitated by starch. Since the amount of PVA required is small, coatings can be prepared which have excellent optical properties such as opacity, brightness and gloss.

In spite of the fact that PVA is a superior pigment binder in some respects, PVA has heretofore been entirely unsatisfactory as a paper coating pigment binder because of certain deleterious characteristics. As a matter of fact, PVA is rarely used for the production of high quality printing coated paper, largely because this does not impart the suitable flow properties to the coating composition. During the mill operation, the coating color is subject to the wide range of shear stresses such as kneading, mixing, pumping up, screening and coating. It is said that the shear stress is about l0 sec". at roll coater and losec pat high speed blade coater. Therefore, the coating color is supposed to maintain a shearing condition. 1 1

Many attemptshave been made to apply aqueous PVA pigment coating color to paper with various types of coating equipment including the roll coater, offset gravure coater, air knife coater and other coaters used in the art. These attempts have been unsuccessful because of the productionof asevere pattern (like orange peel) ,in the coating as it transfers from the coater to the paper. This results in a coating which is rough or streaked. These defects are not smoothed appreciably by supercalendering. The severe pattern makes it impossible to obtain a satisfactory printing job over these coatings. These defects in flow property is increased with the higher degree of polymerization of PVA, and with the higher solids content of coating colors. So, total solidscontent of coating color is relativelylow, as we oftenfind in the successful commercial production. For example, U. S. Pat. No. 2,487,448 discloses coatingcompositions consisting of 50-70 percent kaolinitic, l5-'25 percentby weight of PVA, and 15-25 percent of unswollen starch. Such compositions are representative of what has been used widely in the industry to manufacture laminated paper and paper I board having excellent dry bond strength which do not lose dry bond strength after soaking in water, these coatings are generally applied from an aqueous disperwill 'bereadily recognized that the development of a commercially acceptable PVA for pigment coating color would represent a significant contribution to the paper coating art. In orderto improve the flow property of coating color, various kinds of modification of PVA have so far been tried. However, these attempts have not yet shown satisfactory results in commercial production since this tends to reduce bonding strength in spite of the improvement in flow property. We tried our best and succeeded in improving the flow property without reducing the bonding strength.

An object of this invention is to provide improved paper coating composition. Another object is to provide an improved paper coating compositionwhich can be applied to paper and paper coating to produce a smooth, pattern free coating. A still further object is to provide an improved paper coating composition which can be applied from a relatively high solids content aqueous solution. Another object is to provide an economical coating composition with less binder ratio by using PVA as a single form or as a mixed form with other binders. Still another object is to provide a high quality printing coated paper having an improved optical property. Other objects will be apparent from the following description of this invention.

Aforementioned objects can be achieved by the use of watersoluble modified PVA with hydroxyl groups (-OH) partly replaced by such substituent groups selected from cyanoethyl ether group('OCl-I Cl-i CN), carbamoylethyl ether group (--O--Cl-l CH,CONH,, carboxyethyl ether group (O--CH CH,COOH), sodium carboxyethyl ether group CH,CH,COONa), potassium carboxyethyl ether group (-O-CH,CH ,COOK), 'ammonium' carboxyethyl ether group (-O-ClhClbCOONl-L), carboxymethyl ether group O--CH,COOH), sodium carboxymethyl 'ether group '(--OCH,COONa), potassium carboxymethyl ether group -O-CH COOK), ammonium carboxymethyl ether group (-O-CH, COONI-L).

To produce this water-soluble modified'PVA, we often react PVA with acrylonitrile, acrylamide, monochloric acetic acid, B-propiolactone or alkylester of acrylic acid; For example, the reaction between PVA and acrylonitrile is as shown below.

. o [-OHr-CH-CHr-CH- It will be understood from the above that modified PVA having one kind of substituent group or having simultaneously plural and different kinds of substituent group can respectively be produced with each stage of reaction. The degree of substitution of modified PVA of the invention shows the total quantity of one kind or plural different kinds of substituent groups of modified PVA. For example, the term 4 mol in total-degree of substitution indicates that 4 percent of hydroxyl groups of PVA have been replaced by one kind or plural different kinds of substituent groups. The desirable degree of polymerization p of modified PVA of the invention is at more than 800, which is understood as the most effective range where such characteristic features as bonding strength is clearly shown. And total degree of substitution of modified PVA in the invention shall be in the range between about 2 and 20 mol Modified effect can not been recognized under less than 2 mol condition, and pick resistance of coating during high speed printing operation will be badly affected under more than 20 mol condition, although flow property will be much improved. The most desirable degree of substitution is, therefore, in the range between about 3 and 15 mol'%.

Standardpigments known in the art which are suitable for use in coating colors may be used. Kaolin or clay is generally preferred because'of its desirable pigment characteristics and relatively inexpensive cost. Other pigments such as calcium carbonate, titanium dioxide, aluminum hydroxide, talc, satin white and etc. may also be used. i

A typical example of an improved coating composition of this invention suitable application onto paper for high quality printing paper is shown below.

Example 1 Components Parts by Solid Weight Kaolin 100.0

hydrolysis, total degree of 5.0

substitution of 10 mol cyanoethyl group I0 mol Dow-620 (styrene-butadiene polyme 6.0

Dow Chemical Co.)

Tetrasodium pyrophosphate 0.3

Sufficient water to dilute the coating to 43% total solids content.

This coating color, formulated at about 43 percent solids content in water, issuitable for application by air-knife coater.

Other additives may be used in the formulations to provide specific effects. For example, plasticizer, antiformer, insolubilizer and dyes are often used in these coating colors. Any of these and other materials conventionally used in paper coating may be added to the coating color of the invention.

Coating colors of the invention may be prepared by dissolving the modified PVA in water. A high solid pigment dispersion is separately prepared and then mixed with the PVA solution. In another way, it is possible to make the color by adding the dry modified PVA directrly to the pigment dispersion and then heating to dissolve the 'PVA. This technique of cooking the PVA in the presence of the pigment substantially sometimes increases the binding power of the PVA.

Example 2 Sufficient water to dilute the coating to 60% total solids content.

This coating color is formulated at about 60% solids content in water and is suitable for application by trailing blade coater or roll coater.

In accordance with the above examples, the other coating compositions of the'inventi'on are-quoted as follows: I

Example 3 Components Parts by Solid Weight Kaolin 80.0 Calcium Carbonate 20.0 Modified PVA (=1700, 98-100% hydrolysis, total degree of substitution of 11 mol cyanoethyl group 5 mol carbamoylethyl group 2 mol sodium carboxyethyl group 4 mol 5.0 Dow-620 Latex 5.0 Sodium hexametaphosphate 0.3 Sufficient water to dilute the coating to 60% total solids content.

Example 4 Components 'Parts by Solid Weight Kaolin 100.0 Modified PVA (p=1700, 90% hydrolysis, total degree of 5.0 substitution of 7 mol K2; carbamoylethyl group 3 mol sodium carboxyethyl group 4 mol Dow-620 Latex 5.0 Sodium hexametaphosphate 0.3 Sufiicient water to dilute the coating to 60% total solids content.

Example 5 Components Parts by Solid Weight Kaolin 100.0 Modified PVA (t )=900, 98-100% hydrolysis,-total degree of 7.0 substitution of 5 mol '1); cyanoethyl group. 1 niol carbamoylethyl group 1 mol V carboxyethyl group 3 mol Dow-620 Latex 5.0 Sodium hexametaphosphate 0.3

sufficient water to dilute the coating to 60% total solids content.

Example 6 Components Parts by 1 Solid Weight Kaolin 80.0 Calcium carbonate 20.0 Modified PVA (i=1 700, 98-100% 5.0 hydrolysis, total degree of substitution of 4 mol sodium carboxymethyl group 4 mol 11) Dow620 Latex 5.0 Sodium hexametaphosphate 0.3 Sufficient water to dilute the coating to 60% total solids content.

Example 7 Components Parts by Solid Weight Kaolin 100.0 Modified PVA (i=l700, 98-10096 5.0 hydrolysis, total degree of substitution of 5 mol%; 7 sodium carboxyethyl group 5 mol Dow-620 Latex 5.0 Sodium hexametaphosphate 0.3 Sufiicient water to dilute the coating to 60% total solids content.

Example 8 Components Parts by Solid Weight Kaolin 80.0 Calcium carbonate 20.0 Modified PVA 5 =17oo, 98-100'k hydrolysis, total degree of 5.0 substitution of 15 mol%; carbamoylethyl group 15 mol Dow-620 Latex 5.0 Sodium hexametaphosphate 0.3 Sufficient water to dilute the coating to 55% total solids content.

Example 9 Components Parts by Solid Weight Kaolin 90.0 Satin white 10.0 Modified PVA (=1300, -l00% hydrolysis, total degree of 5.0 substitution of 5 mol k; cyanoethyl group 2 mol carbamoylethyl group 1 mol sodium carboxyethyl group 2 mol %2) Dow-620 Latex 8.0 Sodium hexametaphosphate 0.3 Sufficient water to dilute the coating to 40% total solids content.

Example 10 Components Parts by Solid Weight Kaolin 90.0 Satin white 10.0 Modified PVA (5 d 700, 98-100% hydrolysis. total degree of 5 .0 substitution of 8 mol carbamoylethylgroup 4 mol% sodium carboxyethyl group 4 mol Dow-620 Latex y 8.0 Sodium hexametaphosphate 0.3

Sufficient water to dilute the coating to 40% total 1 solids content.

Aforementioned examples are as per the singular use of modified PVA or its combined use with synthetic resin emulsion. The modified PVA of the invention can also partially replace the coating binders of conventional coating color compositions such as pigmentcasein coating, pigment-casein-synthetic resin emulsion coating, pigment-starch coating, pigment-starchsynthetic resin emulsion coating. This will be economical in that the quantity of binder can be reduced to some extent. The following composition canbe prepared as examples:

Example 1 1 Components Parts by Solid .Weight Kaolin 90.0

Satin white 10.0

Modified PVA (f =l700, 98-100% hydrolysis, total degree of 5.0

substitution of 11 mol carbamoylethyl group 8 mol sodium carboxyethyl group 3 mol Nylgum A-220 (Phosphated Starch, 2.0

Scholten N. V. Netherland) Dow-620 Latex 5.0

Sodium hexametaphosphate 0.3

Sufficient water to dilute the coating to 57% total solids content.

This coating color is formulated at' about 57 percent solids content in water and is suitable for application by blade coater with on-m achine coating.

Example 12 Components 7 Parts by Solid Weight Kaolin 90.0 Satin white 10.0 Modified PVA (p=1700, 98-100% 6.0

hydrolysis, total degree of substitution of 8 mol carbamoylethyl group 4 mol sodium carboxyethyl group 4 mol 'k) Sufficient water to dilute the coating to 42% total solids content.

These coating colors are formulated at about 42% solids content in water andare suitable for application by air-knife coater. I

When the modified pVA of the invention is used as a single coating binder, it is employed in amounts of 3-20 partsper 100 parts ofpigments, and commonly -10 parts per 100 perts-of pigments. 0n the other hand, when modified PVA of the invention is used in combination with other coating binders such as casein, soy protein, starch, synthetic-resin emulsion or mixture thereof, it is employed in amounts l-lS parts and l-20 parts for other binders in proper combination which enables to maintain a practically suitable bonding strength of coating color.

The following examples show PVA of comparison to the coating composition of the invention as a control.

Example 14 Components Parts by Solid Weight Kaolin 100. Unmodified PVA )=l700, 98-l00% 5.0 hydrolysis) Dow-620 Latex 5.0 Sodium hexametaphospha 0.3 Sulficient water to dilute I the coating to 60% total solids content.

Example 15 Components Parts by Solid Weight Kaolin 90.0 Satin white 10.0 Unmodified PVA (F1700, 98-100% 5.0 hydrolysis) Dow-620 Latex I 8.0 Sodium hexametaphosphate 0.3 Sufiicient water to dilute the coating to 40% total solids content.

Example 16 Components Parts by Solid Weight Kaolin 100.0 Modified starch 5.0 Dow-620 Latex 5.0 Sodium hexametaphosphate 0.3 Sufiicient water to dilute the coating to 60% total solids content.

Example 17 Components Parts by Solid Weight Kaolin 100.0 Modified PVA (i=500, 98-l00% 5.0 hydrolysis, total degree of substitution of 9 mol cyanoethyl group 3 mol carbamoylethyl group 1 mol carboxyethyl group 5 mol Dow-620 Latex Sodium hexametaphosphate 0.3

Sufficient water to dilute the coating to 60% total solids content.

In the following table, two methods are used to evaluate the benefits of the coating color of the invention. First is to actually apply the coating colors onto paper using pilot coaters which simulate application of the coating colors by the larger scale commercial coaters and thereafter evaluate the resulting coatings. Second, the [GT printability tester is used to qualitatively evaluate these coatings. This apparatus consists of a rotatable sector to which a strip of the test paper is fastened. A circular disk is arranged to rotate freely in contact with the test paper. The rotatable sector is driven by a spring or pendulum, and when released, rapidly accelerates. The coating color to be tested is applied to the disk. The disk is brought into contact with the sector which is then released and allowed to rotate. Details of this apparatus and procedure are discussed in TAP- Pl, Vol.40, October, 1957 pp 794-801. After the coating color has been applied to the test paper by the lGT apparatus, the applied coating is examined for the presence of split pattern like an orange peel. If a patternfree coating is obtained, the coating color will produce a patternfree coating on commercial equip- Table by Pilot coater By [GT Ex. viscosity coater pattern pattern Pick No. solids (cps) Type Resistance (cm/sec) l 43 l 10 air-knife none none 175 2 60 6000 blade none none 160 3 60 3650 roll none none 165 4 60 2600 roll slight to none none 185 5 60 3000 blade none none 163 6 60 5000 blade slight to none none 170 7 60 5000 blade slight to none none 188 8 55 l 100 champflex slight to none none 185 9 40 100 air-knife none none 165 10 40 120 air-knife none none 168 l l 57 3500 blade slight to none none 170 12 42 160 air-knife none none 165 13 42 105 air-knife none none 185 14 60 4000 roll severe severe 190 15 40 130 air-knife severe severe 177 16 60 2500 roll none none 50 17 v 60 2500 roll none none 68 Specific embodiments of this invention have been set forth in considerable detail, However, many variations not departing from the spirit and scope of this invention will be apparent to those skilled in the art. Accordingly, it is not intended thatthe scope of this invention be limited except as defined in the appended claims.

What we claim are:

1. An article comprising a paper substrate having a pigment coating thereon which coating essentially contains as a coating binder a water-soluble modified polyvinyl alcohol, having an average degree of polymerization of more than 800, having-at least one substituent group selected from the class consisting of cyanoethyl group, carbamoylethyl group, carboxyethyl group, sodium carboxyethyl group, potassium carboxyethyl group, ammonium carboxyethyl group, carboxymethyl group, sodium carboxymethyl group, potassium carboxymethyl group and ammonium carboxymethyl group, and wherein the said water-soluble modified polyvinyl alcohol has a total degree of substitution in the range of about 2 to 20 mol and wherein the said pigment is selected from the group of kaolin, clay, calcium carbonate, talc, titanium dioxide, aluminum hydroxide, satin white andmixtures thereof.

2. An article of claim 1 wherein the said water-soluble modified polyvinyl alcohol is the sole coating binder.

3. An article of claim 2 wherein the said water-soluble modified polyvinyl alcohol is contained in the amounts 3-20 parts by weight per parts of pigment. 

1. An article comprising a paper substrate having a pigment coating thereon which coating essentially contains as a coating binder a water-soluble modified polyvinyl alcohol, having an average degree of polymerization of more than 800, having at least one substituent group selected from the class consisting of cyanoethyl group, carbamoylethyl group, carboxyethyl group, sodium carboxyethyl group, potassium carboxyethyl group, ammonium carboxyethyl group, carboxymethyl group, sodium carboxymethyl group, potassium carboxymethyl group and ammonium carboxymethyl group, and wherein the said water-soluble modified polyvinyl alcohol has a total degree of substitution in the range of about 2 to 20 mol %, and wherein the said pigment is selected from the group of kaolin, clay, calcium carbonate, talc, titanium dioxide, aluminum hydroxide, satin white and mixtures thereOf.
 2. An article of claim 1 wherein the said water-soluble modified polyvinyl alcohol is the sole coating binder. 